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Liquid-liquid equilibria of the system water + acetic acid + 2-hexanone at 25 C and 35 C were studied
to evaluate 2-hexanone as an extraction agent in aqueous solutions of acetic acid. The experimental data
were fitted using the NRTL and UNIQUAC equations. Equilibrium predictions, applying the UNIFAC
method, were also made with the use of liquid-liquid equilibrium specific parameters for both
temperatures.
Introduction
To design the extraction equipment for the separation
of a two-component homogeneous liquid mixture using a
third component, it is necessary to know the liquid-liquid
equilibrium data of the ternary system formed by these
components. These data are also useful when one is
working with a three-component liquid mixture and when
the immiscibility region is to be avoided.
In this work, liquid-liquid equilibrium data of the
system water + acetic acid + 2-hexanone have been
determined at 25 C and 35 C in order to analyze the
viability of 2-hexanone as an extraction agent. The use of
ketones in the recovery of acetic acid from its aqueous
solutions has been previously studied,1-3 using other
ketones of shorter carbon chain.
Experimental Section
2-Hexanone was supplied by Merck and acetic acid by
Carlo Erba. None of the reagents underwent further
purification. Purities specified by the manufacturers were
the following: 2-hexanone, 98%; acetic acid, 99.9%. Distilled water was obtained from the Milli-Q 185 Plus system,
with a resistivity of 18.2 Mcm.
The experimental technique followed to determine the
binodal curve and tie-lines has been previously described.4
The refractive index and density of the phases at equilibrium corresponding to end tie-lines are measured in order
to be able to determine their compositions later on.
Methods based on measurements of physical properties to
determine liquid-liquid equilibrium have been used by
other authors.5-9
The analytical technique followed to determine the
composition of the phases at equilibrium involves preparing
binary mixtures by weight, using a Scaltec SBA31 balance
with a precision of (10-4 g. The third component is added
to these miscible binary mixtures until compositions corresponding to the binodal curve are reached. The maximum
error in the calculation of the compositions of the binodal
curve was estimated to be (10-4. Next, the refractive index
* Author to whom correspondence should be addressed (e-mail
jcorrea@uvigo.es).
Q)
A w
ij
j
i
(1)
i)1 j)1
Journal of Chemical and Engineering Data, Vol. 46, No. 6, 2001 1453
Table 1. Compositions That Determine the Binodal
Curve, Expressed as Mass Fraction (wi), for the System
Water (1) + Acetic Acid (2) + 2-Hexanone (3)
w1
Fx )
min (x
ijk
- x ijk) + Q
2
n
[ ( )]
I
S
+ ln
II
S
(2)
w2
w3
0.9843
0.9354
0.9080
0.8597
0.8139
0.7707
0.7231
0.6814
0.6303
0.5662
0.5183
0.4944
0.4536
0.3891
0.3406
0.2522
0.2038
0.1607
0.1426
0.1178
0.1015
0.0779
0.0640
0.0473
0.0365
0.0222
0.0000
0.0471
0.0730
0.1181
0.1593
0.1973
0.2351
0.2669
0.2992
0.3272
0.3394
0.3449
0.3466
0.3448
0.3420
0.3206
0.2953
0.2624
0.2432
0.2097
0.1835
0.1426
0.1129
0.0765
0.0469
0.0000
T ) 25 C
0.0157
0.0175
0.0190
0.0222
0.0268
0.0320
0.0418
0.0517
0.0705
0.1066
0.1423
0.1607
0.1998
0.2661
0.3174
0.4272
0.5009
0.5769
0.6142
0.6725
0.7150
0.7795
0.8231
0.8762
0.9166
0.9778
0.9859
0.9456
0.9205
0.8910
0.8207
0.7831
0.7178
0.6818
0.6311
0.5860
0.5059
0.4548
0.4167
0.3670
0.3208
0.2861
0.2369
0.2005
0.1717
0.1501
0.1235
0.1041
0.0893
0.0707
0.0527
0.0364
0.0246
0.0000
0.0380
0.0615
0.0897
0.1536
0.1868
0.2410
0.2662
0.2976
0.3196
0.3391
0.3427
0.3419
0.3390
0.3331
0.3257
0.3094
0.2907
0.2692
0.2488
0.2145
0.1842
0.1579
0.1216
0.0797
0.0363
0.0000
T ) 35 C
0.0141
0.0164
0.0180
0.0193
0.0257
0.0301
0.0412
0.0520
0.0713
0.0944
0.1550
0.2025
0.2414
0.2940
0.3461
0.3882
0.4537
0.5088
0.5591
0.6011
0.6620
0.7117
0.7528
0.8077
0.8676
0.9273
0.9754
F/(gcm-3)
nD
0.99501
1.00103
1.00439
1.00968
1.01404
1.01755
1.01969
1.02066
1.01946
1.01320
1.00532
1.00091
0.99137
0.97497
0.96283
0.93622
0.91786
0.90003
0.89126
0.87805
0.86828
0.85405
0.84468
0.83296
0.82421
0.81116
1.33389
1.33715
1.33932
1.34247
1.34583
1.34891
1.35178
1.35491
1.35794
1.36277
1.36577
1.36726
1.36979
1.37447
1.37727
1.38320
1.38638
1.38911
1.39030
1.39189
1.39303
1.39454
1.39543
1.39644
1.39717
1.39797
0.99261
0.99645
0.99906
1.00218
1.00833
1.01110
1.01422
1.01422
1.01226
1.00786
0.99470
0.98300
0.97287
0.96009
0.94737
0.93712
0.92069
0.90766
0.89591
0.88519
0.87156
0.86031
0.85085
0.83854
0.82608
0.81338
0.80270
1.33168
1.33496
1.33661
1.33845
1.34327
1.34559
1.34978
1.35194
1.35521
1.35815
1.36314
1.36653
1.36901
1.37230
1.37524
1.37750
1.38065
1.38244
1.38407
1.38545
1.38704
1.38831
1.38922
1.39030
1.39161
1.39244
1.39326
1454
Figure 2. Binodal curve and tie-lines, experimental (solid line) and calculated using the UNIQUAC equation (dashed line).
Table 2. System Water (1) + Acetic Acid (2) +
2-Hexanone (3): Compositions That Determine Ends of
Tie-Lines, Expressed as Mass Fraction (wi)
aqueous phase
w1
w2
w3
0.933
0.882
0.823
0.787
0.769
0.714
0.642
0.609
0.049
0.097
0.151
0.183
0.198
0.243
0.292
0.310
0.018
0.021
0.026
0.030
0.033
0.043
0.066
0.081
0.941
0.896
0.834
0.800
0.755
0.713
0.664
0.590
0.043
0.085
0.142
0.172
0.211
0.244
0.279
0.316
0.016
0.019
0.024
0.028
0.034
0.043
0.057
0.094
organic phase
nD
w1
w3
nD
T ) 25 C
1.33744
0.034
1.34100
0.047
1.34512
0.069
1.34757
0.084
1.34882
0.093
1.35258
0.121
1.35744
0.169
1.35970
0.190
0.035
0.073
0.125
0.156
0.173
0.216
0.268
0.285
0.931
0.880
0.806
0.760
0.734
0.663
0.563
0.525
1.39730
1.39649
1.39512
1.39415
1.39356
1.39170
1.38860
1.38720
T ) 35 C
1.33526
0.038
1.33824
0.050
1.34229
0.070
1.34452
0.083
1.34743
0.105
1.35006
0.124
1.35317
0.154
1.35782
0.210
0.039
0.070
0.122
0.148
0.188
0.216
0.251
0.294
0.923
0.880
0.808
0.769
0.707
0.660
0.595
0.496
1.39241
1.39170
1.39036
1.38957
1.38820
1.38705
1.38526
1.38197
(%)
F (%)
UNIQUAC
NRTL (Rij ) 0.2)
T ) 25 C
3.04
3.21
1.6
1.2
0.1676
0.1367
UNIQUAC
NRTL (Rij ) 0.2)
T ) 35 C
5.76
4.24
1.5
2.3
0.2190
0.1972
F ) 100
min
(x
ijk
6M
- x ijk)2
(3)
) 100
w2
[ ]
k - k
(4)
FP ) 100
(w
ijk
6M
-w
ijk)2
(5)
Journal of Chemical and Engineering Data, Vol. 46, No. 6, 2001 1455
Figure 3. Binodal curve and tie-lines, experimental (solid line) and calculated using the UNIFAC method (dashed line).
Table 4. Optimized System Specific Parameters of the
UNIQUAC and NRTL Equations for the System Water (1)
+ Acetic Acid (2) + 2-Hexanone (3)a
equation
UNIQUAC
3.04
T ) 25 C
1-2
502.14
1-3
253.03
2-3
-119.54
-388.26
313.62
-57.328
UNIQUAC
5.76
T ) 35 C
1-2
871.39
1-3
603.79
2-3
-194.11
-492.19
199.51
-64.580
equation
NRTL (Rij ) 0.2)
i-j
bij/K
aij/K
aji/K
T ) 25 C
3.21
1-2
1-3
2-3
169.41
1925.4
-533.80
-125.98
189.31
616.57
T ) 35 C
1-2
1-3
2-3
149.35
2013.6
-551.50
-155.57
168.97
488.47
4.24
i-j
bji/K
Literature Cited
(1) Correa, J. M.; Arce, A.; Blanco, A.; Correa, A. Liquid-Liquid
Equilibria of the System Water + Acetic Acid + Methyl Ethyl
Ketone at Several Temperatures. Fluid Phase Equilib. 1987, 32,
151-162.
(2) Blanco, A.; Correa, J. M.; Arce, A.; Correa, A. Liquid-Liquid
Equilibria of the System Water + Acetic Acid + Methyl Propyl
Ketone. Can. J. Chem. Eng. 1988, 66, 136-140.
(3) Correa, J. M.; Blanco, A.; Arce, A. Liquid-Liquid Equilibria of
the System Water + Acetic Acid + Methyl Isopropyl Ketone
between 25 and 55 C. J. Chem. Eng. Data 1989, 34, 415-419.
(4) Otero, J. J.; Comesana, J. F.; Correa, J. M.; Correa, A. LiquidLiquid Equilibria of the System Water + 2-Propanol + 2,2,4Trimethylpentane at 25 C. J. Chem. Eng. Data 2000, 45, 898901.
(5) Coca, J.; Diaz, R. M.; Pazos, C. Extraction of Tretrahydrofuran
from Aqueous Solutions. Ternary Liquid Equilibria with Chloromethanes and Chloroethanes as Solvents. Fluid Phase Equilib.
1980, 4, 125-136.
1456
Received for review March 29, 2001. Accepted July 13, 2001.
JE010108+